Gas Phase Reactions In Organic Synthesis

Flash Vacuum Thermolysis (FVT) techniques have become well-established methods and occupy an increasingly important place in synthesis. Gas Phase Reactions in Organic Synthesis is a complete review of the applications of flash vacuum thermolysis in organic chemistry; it features new developments in FVT, flow thermolysis and vacuum gas-solid reactions which have appeared in scientific literature since 1980.

Offers a physical organic chemistry and mechanistic perspective of the chemistry of thermal processes in the gas phase The book looks at all aspects of the chemical processing technique called gas-phase pyrolysis, including its methodology and reactors, synthesis, reaction mechanisms, structure, kinetics, and applications. It discusses combinations of pyrolytic reactors with physiochemical techniques, routes for and reactions for the synthesis of organic compounds, and the control of reaction rates. Gas-Phase Pyrolytic Reactions: Synthesis, Mechanisms, and Kinetics starts with in-depth chapter coverage of static pyrolysis, dynamic flow pyrolysis, and analytical pyrolysis. It then examines synthesis and applications, including flash vacuum pyrolysis in organic synthesis, elimination of HX, elimination of CO and CO2, pyrolysis of Meldrum’s acid derivatives, and elimination of N2. A chapter on reaction mechanism comes next and includes coverage of retero-ene reaction and reactive intermediates. Following that are sections covering: structure/reactivity correlation, functional group & structural frame interconversions; gas-phase pyrolysis of hydrazones and phosphorus Ylides; and more. Deals with a growing area of chemistry and engineering interest that fits under the practices of green and sustainable chemistry Addresses several important aspects: methodology and reactors, synthesis, reaction mechanisms, structure, kinetics, and applications Reviews general methods of pyrolysis techniques Sets out the fundamentals and advantages of gas-phase pyrolysis in a way that illustrates its wide potential applications Gas-Phase Pyrolytic Reactions: Synthesis, Mechanisms, and Kinetics will appeal to organic chemists, physical organic chemists, chemical engineers and anyone interested in green/sustainable chemistry, chemical synthesis, or process chemistry.

Provides the background, tools, and models required to understand organic synthesis and plan chemical reactions more efficiently Knowledge of physical chemistry is essential for achieving successful chemical reactions in organic chemistry. Chemists must be competent in a range of areas to understand organic synthesis. Organic Chemistry provides the methods, models, and tools necessary to fully comprehend organic reactions. Written by two internationally recognized experts in the field, this much-needed textbook fills a gap in current literature on physical organic chemistry. Rigorous yet straightforward chapters first examine chemical equilibria, thermodynamics, reaction rates and mechanisms, and molecular orbital theory, providing readers with a strong foundation in physical organic chemistry. Subsequent chapters demonstrate various reactions involving organic, organometallic, and biochemical reactants and catalysts. Throughout the text, numerous questions and exercises, over 800 in total, help readers strengthen their comprehension of the subject and highlight key points of learning. The companion Organic Chemistry Workbook contains complete references and answers to every question in this text. A much-needed resource for students and working chemists alike, this text: -Presents models that establish if a reaction is possible, estimate how long it will take, and determine its properties -Describes reactions with broad practical value in synthesis and biology, such as C-C-coupling reactions, pericyclic reactions, and catalytic reactions -Enables readers to plan chemical reactions more efficiently -Features clear illustrations, figures, and tables -With a Foreword by Nobel Prize Laureate Robert H. Grubbs Organic Chemistry: Theory, Reactivity, and Mechanisms in Modern Synthesis is an ideal textbook for students and instructors of chemistry, and a valuable work of reference for organic chemists, physical chemists, and chemical engineers.

The present monograph appears after the death of Professor V. N. Kondratiev, one of those scientists who have greatly contributed to the foundation of contem porary gas kinetics. The most fundamental idea of chemical kinetics, put for ward at the beginning of the twentieth century and connected with names such as W. Nernst, M. Bodenstein, N. N. Semenov, and C. N. Hinshelwood, was that the complex chemical reactions are in fact a manifestation of a set of simpler elementary reactions involving but a small number of species. V. N. Kondratiev was one of the first to adopt this idea and to start investigations on the elementary chemical reactions proper. These investigations revealed explicitly that every elementary reaction in turn consisted of many elementary events usually referred to as elementary processes. It took some time to realize that an elementary reaction, represented in a very simple way by a macroscopic kinetic equation, can be described on a microscopic level by a generalized Boltzmann equation. Neverheless, up to the middle of the twentieth century, gas kinetics was mainly concerned with the interpretation of complex chemical reactions via a set of elementary reactions. But later on, the situation changed drastically. First, the conditions for reducing microscopic cquations to macroscopic ones were clearly set up. These are essentially based on the fact that the small perturbations of the Maxwell-Boltzmann distribution are caused by the reaction proper.

The chapters in this book are devoted to the elementary reactions of small molecules in the gas phase, with some emphasis on reactions important in combustion. The first three chapters cover experimental measurements made at high temperatures, mainly using shock waves and flames; the final chapter describes discharge flow methods near room temperature. The authors-all active in the fields they describe were asked to aim at a level intermediate between a textbook and a review, designed for readers not already familiar with this branch of chemical kinetics. We hope the book will prove especially useful to research workers in related subjects, to research students, and perhaps as source material for the preparation of lectures. The examples have been chosen to illustrate the theoretical basis of the topics rather than attempt a complete coverage. Professors Wagner and Troe describe the remarkable progress made in recent years in measuring dissociation rates for small molecules. Tests ofunimolecular reaction theories are usually made in the 'fall-off' region of pressure: the kinetics change from first order to second order as the pressure is reduced. For large molecules this region lies below atmospheric pressure and is relatively easily accessible. For molecules with four or less atoms, however, the fall-off region lies well above atmospheric pressure: it has been explored using the high pressure shock tube techniques developed by the authors.